CN101733155B - Li-Mg-B-N-H catalytic and reversible hydrogen storage material and preparation method thereof - Google Patents
Li-Mg-B-N-H catalytic and reversible hydrogen storage material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an MCoHx (M=Ti or Zr, x is no less than 1 and no more than 3 catalyst for the reversible hydrogen storage of an Li-Mg-B-N-H hydrogen storage material without a side reaction product and with efficient catalysis and a preparation method thereof as well as an MCoHx catalyst/Li-Mg-B-N-H reversible hydrogen storage material with high hydrogen storage capacity and fast hydrogen adsorption and desorption at lower temperature and a preparation method thereof. The preparation method comprises the following steps of: obtaining an MCoHx catalyst with grain diameter smaller than 100 meshes through induction melting, hydrogenation and dehydrogenation circulation, wherein M=Ti or Zr, and x is no less than 1 and no more than 3; hydrogenating the MCoHx catalyst and Mg powder in a high-pressure hydrogen atmosphere, and ball-milling to obtain catalytic MgH2 powder; then mixing the catalytic MgH2 powder with LiNH2 and LiBH4 according to the mole ratio of 1.0-1.1 to 2 to 0.1-0.3; and carrying out ball-milling complex processing in an argon or nitrogen atmosphere so as to prepare the Li-Mg-B-N-H catalytic and reversible hydrogen storage material. The invention realizes the reversible hydrogen desorption quantity more than 4.6 percent by weight at 150 DEG C and 0.1 MPa.
Description
Technical field
The present invention relates to hydrogen storage material, be specially a kind of through synthetic novel Li-Mg-B-N-H hydrogen storage material of metal hydride catalyst catalysis and preparation method thereof.
Background technology
Hydrogen as a kind of aboundresources, can store and free of contamination secondary energy sources get more and more people's extensive concerning, be described as the green energy resource carrier of 21 century.In whole hydrogen energy system, the storage problem of hydrogen is one of key link of applying of restriction Hydrogen Energy.Storage method commonly used at present has Compressed Gas storage, liquid hydrogen to store and the solid-state storage of hydrogen storage material.Comparatively speaking, adopt the defeated hydrogen of hydrogen storage material storage, have safe and efficient, compact conformation, advantage such as use cost is low is considered to best storage hydrogen mode.The hydrogen storage material of practicability must satisfy that hydrogen-storage density is big, speed for hydrogen absorbing and releasing is fast, operating temperature is moderate, the high requirement of security.With the on-board hydrogen source system, the target that International Energy Agency (IEA) proposes hydrogen storage material is the quality hydrogen-storage density greater than 5%, the volume hydrogen-storage density is greater than 50kg H for fuel cell
2/ m
3, hydrogen discharging temperature is lower than 150 ℃, and cycle life is above 1000 times.Existing hydride hydrogen-storing material perhaps because operating temperature is higher, is difficult to satisfy the needs of practicability perhaps because hydrogen-storage density is on the low side.Therefore, press for research and development novel high-performance hydrogen storage material.
In recent years, brand-new field [P.Chen, a Z.T.Xiong of novel high-capacity hydrogen storage material has been started in the discovery of light metal nitrogen hydride hydrogen-storing material; J.Z.Luo, J.Y.Lin, K.L.Tan; Nature; 2002,420:302], the reversible storage that fracture and the reconstruction of this system material through the N-H key realized hydrogen.The reversible hydrogen storage amount of the Li-Mg-N-H hydrogen storage system of being developed is up to 5.5wt% [Z.T.Xiong, G.T.Wu, J.J.Hu, P.Chen, Advanced Materials, 2004,16:1522; W.F.Luo, J.Alloys Compd., 2004,381:284], but because material suction hydrogen desorption kinetics is very slow, the suction hydrogen discharging temperature of material is generally more than 200 ℃, people such as Jun Yang discover and in the Li-Mg-N-H system, add a small amount of LiBH
4Form novel Li-Mg-B-N-H hydrogen storage material [Jun Yang, Andrea Sudik et al, J.Alloys Compd., 2007,446-447:345], this material has lower hydrogen discharging temperature and faster speed for hydrogen absorbing and releasing.But still exist and to put shortcomings such as the hydrogen operating temperature is higher, cyclical stability difference, had a strong impact on its practical application.Therefore, novel Li-Mg-B-N-H catalyzed reversible hydrogen storage material that exploitation has low operating temperature, height stores hydrogen speed and preparation method thereof has important impetus for the practicalization that promotes this high power capacity storage hydrogen material.
Summary of the invention
The purpose of this invention is to provide a kind of no side reaction product, efficient catalytic Li-Mg-B-N-H hydrogen storage material carries out the reversible MCoH that stores hydrogen
x(M=Ti or Zr, 1≤x≤3) Catalysts and its preparation method, and have high hydrogen storage capability, can under lower temperature, inhale the MCoH of putting hydrogen fast simultaneously
xCatalyst /+Li-Mg-B-N-H reversible hydrogen storage material and preparation method thereof, this material can under relatively mild condition, inhale put hydrogen (150 ℃, 7MPa inhales hydrogen; 150 ℃, 0.1MPa is put hydrogen), the reversible hydrogen storage amount reaches more than the 4.6wt%.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
The reversible hydrogen that stores of a kind of Li-Mg-B-N-H is used metal hydride catalyst, and the chemical expression of this hydride catalytic agent is MCoH
x, wherein M=Ti or Zr, 1≤x≤3.
Described metal hydride catalyst is a graininess, and its particle is less than 100 orders.
The reversible method of storing hydrogen with metal hydride catalyst of a kind of Li-Mg-B-N-H of preparation, this method comprises the steps:
(1) prepare burden according to the MCo stoichiometric proportion, wherein M=Ti or Zr adopt common induction melting prepared MCo alloy, and induction melting carries out under the protection of 0.04～0.1MPa argon gas atmosphere;
(2) MCo alloy mechanical disintegration in air is become-100 order particles, in the stainless steel reaction container of packing into, vacuumize 1.5～3.0h at 450～650 ℃.Be cooled to room temperature afterwards, and in container, charge into the hydrogen of 1.0～3.0MPa purity＞99.99%, keep 0.5～3.0h to make alloy hydride;
(3) alloy is warming up to 450～650 ℃ once more, vacuumizes 1.5～3.0h to accomplish dehydrogenation reaction, is cooled to room temperature afterwards, in container, charges into the hydrogen of 1.0～3.0MPa purity＞99.99% again, keeps 0.5～3.0h to make alloy hydride;
(4) repeating step (3) is accomplished the circulation of 4～7 hydrogenation and dehydrogenation reaction, finally obtains particle less than 100 purpose MCoH
xCatalyst, wherein M=Ti or Zr, 1≤x≤3.
In the preparation method of above-mentioned metal hydride catalyst, in described step (4), preferred hydrogenation and dehydrogenation number of times are 5 times.
A kind of Li-Mg-B-N-H catalyzed reversible hydrogen storage material, this hydrogen storage material is with catalysis MgH
2Powder, LiNH
2And LiBH
4(1.0～1.1) in molar ratio: 2: mix (0.1～0.3), through the composite system of compoundization of ball milling formation, wherein, catalysis MgH
2Powder is by Mg powder and above-mentioned MCoH
xThe multiple catalyzing material that catalyst forms through the hydrogenation ball milling.Need to prove catalysis MgH wherein
2The molal quantity of powder just is meant MgH
2The molal quantity of powder, and disregard the MCoH that uses wherein
xCatalyst carries out the MCoH of catalysis
xCatalyst.
In Li-Mg-B-N-H catalyzed reversible hydrogen storage material of the present invention, MCoH
xCatalyst with the hydrogenation mechanical milling process of Mg powder in be dispersed on the Mg hydride matrix, and form nano-catalytic phase structure, this nano-catalytic phase size＜50nm.
In Li-Mg-B-N-H catalyzed reversible hydrogen storage material of the present invention, MCoH
xCatalyst is 1.0～5.0% with respect to the percentage by weight of hydrogen storage material gross weight.
A kind of Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method, this method may further comprise the steps:
(1) with Mg powder and the above-mentioned MCoH of the present invention
x(wherein M=Ti or Zr, 1≤x≤3) catalyst carries out the hydrogenation ball-milling treatment in hydrogen atmosphere, wherein, and MCoH
xCatalyst consumption with respect to the percentage by weight of the hydrogen storage material gross weight that will prepare be 1.0～5.0%;
(2) with catalysis MgH
2Powder, LiNH
2And LiBH
4(1.0～1.1) in molar ratio: 2: mix (0.1～0.3), in argon gas or nitrogen atmosphere, carries out the processing of compoundization of ball milling, processes Li-Mg-B-N-H catalyzed reversible hydrogen storage material.
In above-mentioned step (1), Mg powder and MCoH
xThe granularity of catalyst fines is respectively-200 orders and-100 orders.
The hydrogenation ball-milling treatment adopts the reaction ball milling technology of high pressure hydrogen atmosphere.In described step (1), the Hydrogen Vapor Pressure scope is 0.5～5.0MPa; The ball milling time is 2～50 hours, and ball material weight ratio is 1: 1～50: 1.Concrete operations are: with Mg powder, MCoH
xCatalyst fines and abrading-ball place in the ball grinder, charge into hydrogen after vacuumizing and carry out ball milling, and ball milling 1～5 hour inspection jar internal pressure at interval changes, and hydrogen make-up is to keep a jar interior hydrogen pressure.
The ball-milling technology of argon gas or nitrogen atmosphere protection is adopted in compoundization processing.In described step (2), argon gas or nitrogen gas pressure scope are 0.1～5.0MPa; The ball milling time is 2～50 hours, and ball material weight ratio is 1: 1～50: 1.Concrete operations are: with catalysis MgH
2Powder, LiNH
2, LiBH
4Place in the ball grinder with abrading-ball, charge into argon gas or nitrogen protection gas after vacuumizing and carry out the processing of compoundization of ball milling, keep the protection atmospheric pressure in the mechanical milling process and be higher than 0.1MPa, finally obtain Li-Mg-B-N-H catalyzed reversible hydrogen storage material with reactive metal in the protective pot.
In above-mentioned Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method, in described step (1), MCoH
xThe addition of catalyst preferably with respect to the hydrogen storage material gross weight that will prepare be 3wt%, Hydrogen Vapor Pressure is preferably 3MPa, the ball milling time is preferably 30h, ball material weight ratio is preferably 15.: 1.
In above-mentioned Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method, in described step (2), the ball milling time is preferably 10h, and ball material weight ratio is preferably 15.: 1.
Advantage of the present invention is:
MCoH through induction melting, hydrogenation and dehydrogenation cycle preparation
xCatalyst (wherein M=Ti or Zr, 1≤x≤3) particle, metal catalytic constituent element content is high; Alloy fragility is good, with Mg powder hydrogenation ball milling and subsequently compoundization process in, being distributed in the Li-Mg-B-N-H hydrogen storage material matrix of catalyst granules even dispersion; Order does not have side reaction product and forms; Can realize the Li-Mg-B-N-H hydrogen storage material at 150 ℃, put hydrogen under the 0.1MPa condition fast, the reversible hydrogen storage amount is more than 4.6wt%.
Table in the following description of drawings and the specific embodiment in the represented Li-Mg-B-N-H catalyzed reversible hydrogen storage material is answered formula, as: (2LiNH
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3Hydrogen storage material, chemical formula LiNH wherein
2, MgH
2And LiBH
4Numeral 2,1.1 before and 0.1 expression LiNH
2, MgH
2And LiBH
4Between mol ratio; ZrCoH
3The percentage 3wt% of weight before is MCoH
3The percentage with respect to the hydrogen storage material gross weight of catalyst.
Description of drawings
Fig. 1 is ZrCoH among the embodiment 1
3Alloy hydride XRD figure spectrum.
Fig. 2 is (2LiNH among the embodiment 3
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3Hydrogen storage material and the 2LiNH that does not add catalyst
2-1.1MgH
2-0.1LiBH
4Hydrogen storage material is at 150 ℃, the suction hydrogen kinetic curve comparison diagram under the 0.1MPa condition.
Fig. 3 is (2LiNH among the embodiment 3
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3Hydrogen storage material microstructure and Zr, Co element distribute can spectrogram.
Fig. 4 is (2LiNH among the embodiment 4
2-1.1MgH
2-0.1LiBH
4)/5wt%ZrCoH
3Hydrogen storage material and the 2LiNH that does not add catalyst
2-1.1MgH
2-0.1LiBH
4Hydrogen storage material is at 150 ℃, the hydrogen desorption kinetics curve comparison diagram under the 0.1MPa condition
Fig. 5 is (2LiNH among the embodiment 5
2-1.0MgH
2-0.3LiBH
4)/1wt%ZrCoH
3Hydrogen storage material is at 150 ℃, and the hydrogen kinetic curve is inhaled in the circulation under the 7.0MPa condition.
Fig. 6 is (2LiNH among the embodiment 6
2-1.1MgH
2-0.1LiBH
4)/3wt%TiCoH
xHydrogen storage material is at 150 ℃, the hydrogen desorption kinetics curve under the 0.1MPa condition.
The specific embodiment
MCoH of the present invention
x(M=Ti or Zr, 1≤x≤3) Catalysts and its preparation method, MCoH
x(M=Ti or Zr; 1≤x≤3) catalyst efficient catalytic Li-Mg-B-N-H reversible hydrogen storage material and preparation method thereof; In following embodiment 1-6, according to stoicheiometry, the synthetic method of each embodiment material and carry out performance test and characterize, but the present invention is not limited in present embodiment.
Take by weighing purity＞99.9% raw material at 1.: 1 by Zr and Co mol ratio, adopt induction melting method molten alloy, system is evacuated to 10 before the melting
-2～10
-3Pa charges into 0.04～0.1MPa argon shield afterwards, through 3 meltings overturn the ZrCo alloy.Alloy pig mechanical disintegration in air is become-100 order particles; Pack in the stainless steel reactor; Carry out 4～7 450～650 ℃ of circulations that vacuumize 1.5～3.0h and room temperature 1.0～3.0MPa hydrogen hydrogenase 10 .5～3.0h; Gained hydride powder XRD figure spectrum is as shown in Figure 1, for particle diameter less than 100 purpose ZrCoH
3The hydride particle powder.
Take by weighing purity＞99.9% raw material at 1.: 1 by Ti and Co mol ratio, adopt induction melting method molten alloy, system is evacuated to 10 before the melting
-2～10
-3Pa charges into 0.04～0.1MPa argon shield afterwards, through 3 meltings overturn the ZrCo alloy.Alloy pig mechanical disintegration in air is become-100 order particles, in the stainless steel reactor of packing into, carry out 4～7 450～650 ℃ of circulations that vacuumize 1.5～3.0h and room temperature 1.0～3.0MPa hydrogen hydrogenase 10 .5～3.0h, get particle diameter less than 100 purpose TiCoH
10The hydride particle powder.
With ZrCoH synthetic among the embodiment 1
3Mix by weight 10: 90 with-200 order Mg powder, put into ball grinder with abrading-ball, vacuumize that (vacuum is superior to 1 * 10 by ratio of grinding media to material 15: 1
-2Pa) charge into 3MPa hydrogen after and carry out reaction ball milling, ball milling 5 hours inspection jar internal pressures at interval changes, and hydrogen make-up is to keep a jar interior hydrogen pressure, and ball milling 30 hours makes the complete hydrogenation of Mg powder generate MgH
2
With compound ZrCoH
3The MgH of catalyst
2Powder and LiNH
2, LiBH
4Mixed in 1.1: 2: 0.1 in molar ratio, wherein ZrCoH
3Catalyst accounts for the 3wt% of raw material gross weight, and ratio of grinding media to material 15: 1 vacuumizes that (vacuum is superior to 1 * 10
-2Pa) charge into 0.2MPa argon shield gas after and carry out compoundization ball milling, ball milling 10 hours obtains (2LiNH
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3Composite hydrogen storage material.
Comparative example 1
With MgH
2With LiNH
2, LiBH
4Mixed in 1.1: 2: 0.1 in molar ratio, and carried out compoundization ball milling, obtain 2LiNH by the milling parameters of embodiment 3
2-1.1MgH
2-0.1LiBH
4Composite hydrogen storage material.
Sample in embodiment 3 and the comparing embodiment 1 is carried out hydrogen storage property to be tested on the same stage.Shown in Figure 2ly be respectively sample in embodiment 3 and the comparing embodiment 1 at 150 ℃, to the hydrogen desorption kinetics curve of 0.1MPa.Thus it is clear that, (the 2LiNH of the present invention's preparation
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
360 minutes hydrogen desorption capacity of composite hydrogen storage material reaches 3.72wt%, and the hydrogen desorption capacity of 10h is 4.65wt%, and does not add ZrCoH
3The 2LiNH of catalyst
2-1.1MgH
2-0.1LiBH
4Hydrogen storage material hydrogen desorption capacity of 60 minutes under similarity condition has only 1.71wt%, and the hydrogen desorption capacity of 10h is 3.45wt%.(the 2LiNH of the present invention's preparation
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3The hydrogen discharging rate and the capacity of composite hydrogen storage material are significantly increased.
Shown in Figure 3 is the (2LiNH of embodiment 3 preparations
2-1.1MgH
2-0.1LiBH
4)/3wt%ZrCoH
3The microstructure of composite hydrogen storage material reaches wherein Zr, Co distribution diagram of element, and is visible, ZrCoH
3Catalyst phase particle size shows ZrCoH less than 50nm and Zr, be distributed in the matrix of composite hydrogen storage material to the Co even dispersion
3Catalyst and Li-Mg-B-N-H reactant matrix are fully compound, thereby have played good catalytic action.
Be with embodiment 3 differences:
When Mg powder hydrogenation ball-milling treatment, increased ZrCoH by proper proportion
3The content of catalyst, ZrCoH in the composite hydrogen storage material of feasible preparation
3Catalyst accounts for the 5wt% of raw material gross weight, and during the processing of compoundization of ball milling, ratio of grinding media to material is 10: 1, the 0.5MPa nitrogen protection, and ball milling 15 hours obtains (2LiNH
2-1.1MgH
2-0.1LiBH
4)/5wt%ZrCoH
3Composite hydrogen storage material.In addition, other process conditions are all identical with embodiment 3.
Comparative example 2
With MgH
2With LiNH
2, LiBH
4Mixed in 1.1: 2: 0.1 in molar ratio, and carried out compoundization ball milling, obtain 2LiNH by the milling parameters of embodiment 4
2-1.1MgH
2-0.1LiBH
4Composite hydrogen storage material.
Sample in embodiment 4 and the comparing embodiment 2 150 ℃ of at first dehydrogenations, is tested its hydrogen sucking function then.Shown in Figure 4ly be respectively sample in embodiment 4 and the comparing embodiment 2 at 150 ℃, the suction hydrogen kinetic curve under the 7.0MPa hydrogen pressure.Thus it is clear that, (the 2LiNH of the present invention's preparation
2-1.1MgH
2-0.1LiBH
4)/5wt%ZrCoH
310 minutes hydrogen of composite hydrogen storage material reaches 5.26wt%, and does not add ZrCoH
3The 2LiNH of catalyst
2-1.1MgH
2-0.1LiBH
4Hydrogen storage material hydrogen of 10 minutes under similarity condition has only 2.84wt%, (the 2LiNH of the present invention's preparation
2-1.1MgH
2-0.1LiBH
4)/5wt%ZrCoH
3The hydrogen-absorption speed and the capacity of composite hydrogen storage material are significantly increased.
Be with embodiment 3 differences:
When Mg powder hydrogenation ball-milling treatment, reduced ZrCoH by proper proportion
3The content of catalyst, ZrCoH in the composite hydrogen storage material of feasible preparation
3Catalyst accounts for the 1wt% of raw material gross weight, during the processing of compoundization of ball milling, and MgH
2, LiNH
2And LiBH
4Mol ratio 1.0: 2: 0.3, ratio of grinding media to material is 30: 1, the 0.1MPa argon shield, ball milling 30 hours obtains (2LiNH
2-1MgH
2-0.3LiBH
4)/1wt%ZrCoH
3Composite hydrogen storage material.In addition, other process conditions are all identical with embodiment 3.
Sample among the embodiment 5 150 ℃ of at first dehydrogenations, is tested its hydrogen sucking function then, and repeatedly inhale and put hydrogen circulation.Shown in Figure 5 is that sample among the embodiment 5 is at 150 ℃, to the circulation hydrogen desorption kinetics curve of 0.1MPa.The first, the 5th and the tenth hydrogen desorption capacity in 10b is respectively 4.52,4.40 and 4.26wt%, and it is less that the hydrogen capacity decay is put in the material circulation, shows good suction and put the hydrogen cyclical stability.
With TiCoH synthetic among the embodiment 2
1.0Mix by weight 10: 90 with-200 order Mg powder, put into ball grinder with abrading-ball, vacuumize that (vacuum is superior to 1 * 10 by ratio of grinding media to material 15: 1
-2Pa) charge into 3MPa hydrogen after and carry out reaction ball milling, ball milling 5 hours inspection jar internal pressures at interval changes, and hydrogen make-up is to keep a jar interior hydrogen pressure, and ball milling 30 hours makes the complete hydrogenation of Mg powder generate MgH
2
With composite Ti CoH
1.0The MgH of catalyst
2Powder and LiNH
2, LiBH
4Mixed in 1.1: 2: 0.1 in molar ratio, wherein TiCoH
1.0Catalyst accounts for the 3wt% of raw material gross weight, puts into ball grinder by ratio of grinding media to material 15: 1 with abrading-ball, vacuumizes that (vacuum is superior to 1 * 10
-2Pa) charge into 0.2MPa argon shield gas after and carry out compoundization ball milling, ball milling 10 hours obtains (2LiNH
2-1.1MgH
2-0.1LiBH
4)/3wt%TiCoH
1.0Composite hydrogen storage material.Shown in Figure 6 be its at 150 ℃, to the hydrogen desorption kinetics curve under the 0.1MPa hydrogen pressure, its hydrogen desorption capacity in 60min reaches 3.3wt%, accounts for more than 80% of total hydrogen desorption capacity, shows good hydrogen discharging performance.
Claims (6)
1. Li-Mg-B-N-H catalyzed reversible hydrogen storage material, it is characterized in that: this hydrogen storage material is with catalysis MgH
2Powder, LiNH
2And LiBH
4(1.0～1.1) in molar ratio: 2: mix (0.1～0.3), through the composite system of compoundization of ball milling formation, and said catalysis MgH
2Powder is by Mg powder and MCoH
xThe multiple catalyzing material that catalyst forms through the hydrogenation ball milling, wherein M=Ti or Zr, 1≤x≤3.
2. Li-Mg-B-N-H catalyzed reversible hydrogen storage material according to claim 1 is characterized in that: MCoH
xCatalyst is 1.0～5.0% with respect to the percentage by weight of hydrogen storage material gross weight.
3. Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method, it is characterized in that: this method comprises the steps:
(1) with Mg powder and MCoH
xCatalyst carries out the hydrogenation ball-milling treatment in hydrogen atmosphere, wherein M=Ti or Zr, 1≤x≤3, MCoH
xCatalyst consumption with respect to the percentage by weight of the hydrogen storage material gross weight that will prepare be 1.0～5.0%;
(2) with the catalysis MgH for preparing in the step (1)
2Powder and LiNH
2And LiBH
4(1.0～1.1) in molar ratio: 2: mix (0.1～0.3), in argon gas or nitrogen atmosphere, carries out the processing of compoundization of ball milling, processes Li-Mg-B-N-H catalyzed reversible hydrogen storage material.
4. Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method according to claim 3 is characterized in that: in described step (1), and Mg powder and MCoH
xThe granularity of catalyst fines is respectively-200 orders and-100 orders.
5. Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method according to claim 3 is characterized in that: in described step (1), the Hydrogen Vapor Pressure scope is 0.5～5.0MPa; The ball milling time is 2～50 hours, and ball material weight ratio is 1: 1～50: 1.
6. Li-Mg-B-N-H catalyzed reversible hydrogen storage material preparation method according to claim 3 is characterized in that: in described step (2), argon gas or nitrogen gas pressure scope are 0.1～5.0MPa; The ball milling time is 2～50 hours, and ball material weight ratio is 1: 1～50: 1.
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| CN102059090B (en) * | 2011-01-12 | 2012-11-21 | 浙江大学 | CaF2-doped LiBH4 reversible hydrogen storage material with high hydrogen storage quantity and preparation method thereof |
| CN103183312B (en) * | 2011-12-26 | 2015-06-17 | 北京有色金属研究总院 | Li-Mg-B-N-H hydrogen storage material |
| CN102807191B (en) * | 2012-09-06 | 2014-10-01 | 沈阳师范大学 | Method for synthesizing Li-Mg-B-H hydrogen storage material |
| CN103264159B (en) * | 2013-05-29 | 2014-12-31 | 上海大学 | Method for achieving rapid hydrogen desorption of MgH2 under microwave |
| CN105039815B (en) * | 2015-08-20 | 2017-03-22 | 广西大学 | Preparation method of Mg-Li solid solution hydrogen storage material |
| US9533884B1 (en) | 2016-05-24 | 2017-01-03 | Kuwait Institute For Scientific Research | Composition for hydrogen storage |
| CN113856670B (en) * | 2021-08-16 | 2023-11-24 | 广东省科学院资源利用与稀土开发研究所 | Catalytic MgH 2 Composite oxide for rapid hydrogen release and application thereof |
| CN115325441B (en) * | 2022-08-24 | 2023-11-24 | 浙江浙能航天氢能技术有限公司 | Hydrogen precooler testing system and method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974830A (en) * | 2006-12-01 | 2007-06-06 | 南开大学 | Hydrogen-storing material and its prepn process and application |
| CN101353733A (en) * | 2008-08-07 | 2009-01-28 | 上海交通大学 | Preparation of La-Mg-Ni system hydrogen occluding alloy |
-
2009
- 2009-12-09 CN CN2009102418181A patent/CN101733155B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974830A (en) * | 2006-12-01 | 2007-06-06 | 南开大学 | Hydrogen-storing material and its prepn process and application |
| CN101353733A (en) * | 2008-08-07 | 2009-01-28 | 上海交通大学 | Preparation of La-Mg-Ni system hydrogen occluding alloy |
Non-Patent Citations (4)
| Title |
|---|
| JP昭57-56301A 1982.04.03 |
| Jun Yang et al..Hydrogen storage properties of 2LiNH2 + LiBH4 +MgH2.《Journal of Alloys and Compounds》.2007,第446-447卷第345－349页. * |
| LI Hualing et al..Preparation and research on poisoning resistant Zr-Co based hydrogen storage alloys.《RARE METALS》.2008,第27卷(第4期),第367-370页. * |
| 蒋刚等.气固氢化反应热力学函数计算的近似方法.《原子核物理评论》.2002,第19卷第91-94页. * |
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